A novel class of amide-derived air-stable P,O-ligands for Suzuki cross-coupling at low catalyst loading

The benzamide-derived P,O-ligands efficiently promoted the Pd-catalyzed Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid at 0.01 mol % of Pd loading at 60-80 °C to form biaryls in excellent yields. A sterically hindered arylboronic acid gave a quantitative yield of the coupling product at 110 °C with 1 mol % Pd.     

不饱和链烃沸点的拓扑研究

基于邻接矩阵与边价 (fi)定义边价连接性指数 ( mF) ,其中的0 F ,1 F与 2 94种不饱和链烃 (包括烯烃、炔烃及烯炔烃 )的沸点 (Tb)关联 ,得到良好的数学模型 :ln( 70 0 -Tb) =6 5 2 3 3 1-0 0 0 4880 F2 -0 3 46771 F0 5(n =2 94,R =0 9979,R2 =0 995 8,F =3 490 4,S =5 12 ) ,该回归模型经Jackknife法检验具有总体稳健性 .可以预示 ,该指数将在定量构效关系研究中成为重要参数 .     

Synthetic applications of aryl radical building blocks for cyclisation onto azoles

2-(2-Bromophenyl)ethyl groups have been used as building blocks in radical cyclisation reactions onto azoles to synthesise tri- and tetra-cyclic heterocycles. 2-(2-Bromophenyl)ethyl methanesulfonate was used to alkylate azoles (imidazoles, pyrroles, indoles and pyrazoles) for the synthesis of the radical precursors. Cyclisations of the intermediate aryl radicals yield new 6-membered rings attached to the azoles. The aryl radicals undergo intramolecular homolytic aromatic substitution onto the azole rings. Tributylgermanium hydride has been used with success to replace the toxic and troublesome tributyltin hydride. Initial studies show that the protocol can be used on solid phase resins. The molecular and crystal structures of methyl 5,6-dihydroimidazo[5,1-a]iso-quinoline-1-carboxylate and methyl 5,6-dihydroimidazo[2,1-a]isoquinoline-3-carboxylate were determined by X-ray crystallography.     

锆对铂重整催化剂性能的影响规律

以正庚烷的转化为探针反应 ,研究了添加元素锆对铂重整催化剂性能的影响规律。结果表明 ,在 4 50℃和连续流动条件下 ,Pt/γ -Al2 O3催化剂中引入锆不仅能够提高铂催化剂的稳定性和芳构化产率、抑制氢解和异构化 ,而且能使铂催化剂保持初活性。锆含量在 0 .56%左右 ,其调变作用最为显著。     

Supramolecular assemblies from single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles

Three types of single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles were synthesized.They readily formed different kinds of organized supramolecular assemblies,including vesicles,tapes,and micellar fibers,in aqueous solution.The aggregates morphology was characterized by transmission electron microscopy (TEM) after negative staining.The superstructures of these aggregates seemed to be determined by the geometry and the head group's properties of the corresponding amphiphiles.     

On the reaction of 4-substituted trimethyltin aromatics with perchlorylfluoride

To evaluate the suitability of [¹⁸F]perchorylfluoride [¹⁸F]FClO₃ as an electrophilic fluorination agent for the preparation of radiopharmaceuticals, the reactivity non-radioactive FClO₃ towards 4-substituted trimethyltin aromatic compounds was studied. Contrary to the expectation, an electrophilic fluorination of the aromatic nucleus did not occur. The reaction of perchlorylfluoride with aromatic trimethylstannyl compounds resulted in the formation of trimethyltin fluoride and the respective destannylated aromatics in variable yields.     

STUDIES OF THE HOMOLOGATION OF METHANE ONSUPPORTED TRANSITION METAL CATALYSTS

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Steroid Cyclophanes as Artificial Cell-surface Receptors. Molecular Recognition and its Consequence in Signal Transduction Behavior

Steroid cyclophanes, bearing four bile acid moieties covalently placed on a tetraazaparacyclophane skeleton, were designed and synthesized as artificial cell-surface receptors. Guest-binding behavior of the steroid cyclophanes embedded in a bilayer membrane formed with a synthetic peptide lipid was clarified by means of fluorescence and circular dichroism spectroscopy. We found that the steroid cyclophane effectively bound aromatic guests in both bilayer membranes and aqueous solution. In addition, copper(II) ions acted as a guest species for the steroid cyclophane and a competitive inhibitor toward a NADH-dependent lactate dehydrogenase (LDH). On these grounds, we constituted a supramolecular assembly as an artificial signaling system in combination with the steroid cyclophane, a cationic peptide lipid, and LDH. As a consequence, the steroid cyclophane acted as an effective artificial cell-surface receptor being capable of transmitting an external signal to the enzyme in collaboration with copper(II) ions as a signal transmitter.     

Serendipitous synthesis of a ditwistane: a one-step access!

4-tert-Butyl-2-cyclohexen-1-one dimerizes in THF solution via its kinetic enolate, leading to di-tert-butylditwistane 8 in up to 36% yield (−78 °C → room temp., protonolysis, flash chromatography). X-ray crystallography shows that 8 incorporates one R and one S enantiomer of the starting ketone; none of the diastereomeric ditwistanes epi-8, epi’-8 or iso-8 was isolated. This means that the formation of 8 proceeds with mutual kinetic resolution and 100% induced diastereoselectivity.     

Studies on the Chemistry of Thienoannelated O , N - and S , N -Containing Heterocycles, 28 [1]. Synthesis of Imidazo[1,5- d ]thieno[2,3- b ][1,4]thiazine Derivatives as GABA -Receptor Ligands

Summary.  GABA-receptor-ligands are still very interesting in drug-development. Usually benzodiazepines are used in the treatment but they have serious side-effects. Thus, a recently synthesized quioxaline derivative which showed reduced side-effects in an animal model was used as a model-substance. The cyclus was modified to optimize the pharmacological profile. Accordingly, a series of imidazo-thieno-thiazines was synthesized starting from 5-acetyl-2-chloro-3-nitrothiophene to yield 6-ethyl-2,3-dihydro-1H-thieno[2,3-b][1,4]thiazine-2-one. Reaction with potassium tert-butoxide and diethylchlorophosphate gave an intermediate, which resulted in the desired ring system after adding the corresponding isocyanides and potassium tert-butoxide. Corresponding author. E-mail: thomas.erker@univie.ac.at Received August 6, 2002; accepted August 13, 2002